Tertiary-amino-2-aryl-2-(4-quinolyl) alkane-nitriles and their preparation



a of preferably 6-10 carbon atoms.

Patented Oct. 9, 1951 UNITED STATES PATENT OFFICE TERTIARY-AMINO- 2 -ARYL- 2 4 QUIN- OLYL)ALKANE-NITRILES AND THEIR PREPARATION Alexander R. Surrey, Albany County, and Royal A. Cutler, Rensselaer- County, N. Y., assignors to Sterling Drug Inc., Wilmington, .DeL; a; corp j c poration of Delaware No Drawing. Application May 28, 1948, Serial No. 29,936

- 14 claims. (61. 260-286) More particularly, 'this invention relates to basic alpha-aryl alpha-(4 quinolyllalkanenitriles, to derivatives 1th'e'reof,"to addition salts of hereinbefore named compounds; 7 Our invention comprehends compounds of the formula where B is a lower aliphatic tertiary-amino radical; X is a lower alkylene radical; Y is a member of the group consisting of CN, CONI-Iz, and H; A is an;aryl radical; and Q isa 4- quinolyl radical. Thesecompounds are of interest as pharmaceutical agents and as intermediates in preparing pharmaceutical agents.

In the above formula, the lower aliphatic tertiary-amino radical, designated as B, comprehends lower dialkylamino radicals illustrated by examplessuch as dimethylamino, diethylamino, ethylmethylamino, di-n-butylamino, and the like; and lower saturated N-heterocyclic radicals'illustrated by examples such as 1piperidyl, 4'-morpholinyl, 3-methy1-1-piperidyl, 2-methyl-1-pyrvI'olidyl, 2,6-dimethyl-1-piperidyl, and, the like.

In other words, BH designates, a lower aliphatic secondary-amine as illustrated by die'thylamine, di-n-butylamine, morpholine, 3-ethylpiperidine, and the like. The lower alkylene'radical, desig- I nated as X, includes radicals such as and the like. cals interrupted by elements such as oxygen and sulfur, e. g. I l r l ,l

Thus, the expression "a lower aliphatic tertiaryaminoalkyl radical when used hereafter in the specification or in the appended claims, comprehends those groups designated as B-X--, where B and X have the meanings hereinabove described. The aryl radical, designated as A, is one cal can be substituted by such groups as hydroxyl; alkoxyl such as methoxyl, ethoxyl, -etc.; dialkylamino such as dimethylamino; halogen such as chloro, bromo, or iodo; lower al yl such invention relates to uuinoline compounds l and to'processes of preparing the same.

"5 said compounds, and to processes ofp'reparing the The aryl radipropoxy, and the like; aryloxy, such as phenoxy;

aralkoxy, such as benzyloxy; trihaloalkyl, such as trifluoromethyl; nitro; amino; substitutedamino, such as acetylamino, ethylamino, dimethylamino, benzylamino, and the like; and other substituents.

illustrative of our invention the following specific compounds arepr'esentedz' I l 1. 6-diethylamino-2-' (4 methoxyphenyl) -2 (fi-methoxyA-quinolyl) hexanenitrile,

OCHl

CHIO V 2. 4-dimethylamino -2- (3 methylphenyl) 2 (3-methyl-8-ethoxy-e-quinolyl) pentanenitrlle,

i @CH 7 (onmrrcnorn- -CN 7 43H: 7 I

, 3 3. 5-(l-piperidy1) -2-pheny1-2- (3 bromo 7 chloro-4-quinoly1) pentanamide,

CHz-C :5. 3' (4 morpholinyl) -1-phenyl-1-(,3',6,7--tri.- :n'aethyl-4-quinoly1) -propane.

CH: CH1

CH3 6. 4 (2 methyl-l-py-rrolidyl)-1-phenyl-;1-('lphenoxyi-quinelyl) -butane,,

In addition, our invention comprehends processes for preparing the above compounds. These processes, are presented in the following chart, wherein B, X, A, and Q have the meanings hereinabove specified, and Z stands for halogen:

Cfhartl I I n m phenylacetonitrile;

4-quinolyDbutanenitrile is prepared by condensing 4,7-dichloroquinoline with 4-diethylamino- Z-phehylbutanenitrile in the presence of sodium amide. Other basic condensing agents, e. g. po-

tassium. amide, sodium hydride, phenyllithium,

and the like, can be used in place of sodium amide.

' The intermediate tertiary-amino-2-ary1alkanenitriles (II) are a generally known group of compounds, which are prepared by condensing in the presence of a basic agent, such as sodium amide, a, lower aliphatic tertiary-aminoalkyl halide, 'B-X-halogen, with an arylacetonitrile, ACHzCN, where B, X, and A have the meanings herei'nabove specified. For example, the preparation of 4-diethylamino-2-phenylbutanenitrile from Z-diethylaminoethyl chloride and phenylacetonitrile is described by Eisleb, Ber. '74, 1441 (1941). Other examples are afforded by Kwartler and Lucas (J. A. C. S. 68, 2395 (1946)) who describe the preparations of: 4-diethy1a-mino-2- (4-chlorophenyl.)butanenitrile from '2diethyl'- 'aminoethyl chloride and 4-ch1orophenylacetoni tril'e 4-diethylamino-2 (3,4-dichlorophenyl) butanenitrile from Z-diethylaminoethyl chloride and 3,4-dichlorophenylacetonitrile; 4-diethylamino -2- (4-methoxyph'eny'l) butanenitrile from 2-di'ethylaminoethyl chloride and 4-methoxy- 4-dimethylamino-2-pheny1 butanenitrile from 2-dimethylaminoethyl chloride and phenylacetonitrile; and 5-diethylamino- 2-(4-ch1orophenyl)pentanenitrile from B-dieth- I ylaminopropyl chloride and 4-chlorophenylaceto- 4-ChIoro-T-iodoquinoline 4,7-dichloro-6-methoxyquinoline 4,5-d ehloroquinoline 3-nitro-4-chloroquinoline 3-amino-4-chloroquinoline 4-ch1oro-7-fiuoroquinoline 4-ch1oro-7-trifluoromethylquinoline 4,7 -dichloro--methoxyquinoline 4-chloro-7-phenoxyquino1ine 3,4-dibromoquinoline 4-chloro-6-nitrcquinoline Step (2) of Chart I can be carried out by various methods. In our hands the best results are obtained when a concentrated sulfuric acid solution of the basic nitrile, In, is allowed to stand at room temperature for an extended period. Thus, yields of 90% or better of 4-diethylamino 2 phenyl 2 (7 chloro 4- quinolyhbutanamide are obtained by allowing the sulfuric acid solution of the corresponding nitrile to stand at room temperature for about five weeks. The hydrolysis of the nitrile to the amide, step (2), also can be performed, but in lower yields, by refluxing the appropriate nitrile with sodium hydroxide in aqueous ethanol (about 70%) for about twelve hours or with aqueous sulfuric acid (about 60%) for one hour.

Step (3) of Chart I, the complete hydrolysis of the nitrile group to the carboxyl group which spontaneously loses carbon dioxide, is effected by refluxing an aqueous sulfuric acid (about 60%) solution of the nitrile, III, for twelve hours or longer to give practically quantitative yields of the basic quinoline derivative designated as V in Chart I. For example, in such a manner 3-diethylamino 1 phenyl-l-(7-chloro-4-quinolyl)propane is prepared from 4-diethylamino-2- phenyl-2- ('7-ch1oro-4-quino1y1) butanenitrile.

Step (4) of Chart I, the conversion of the carboxamides designated as IV to the related basic quinoline derivatives designated as V is eflected in the same manner that step (3) is carried out. Thus, as a specific example, 3-diethylamino 1 phenyl-l-(7-chloro-4-quinolyl) propane is prepared from 4-diethylamino-2-phenyl- 2- ('l-chloro-4-quinolyl) butanamide.

Our invention comprehends, not only the basic quinoline derivatives (III, IV and V of Chart I) already described and processes of preparing the same, but also their salts with non-toxic inorganic or organic acids and with esters of strong inorganic acids and organic sulfonic acids. Among the acids which may be employed to form the salts are hydrochloric acid, phosphoric acid, sulfuric acid, sulfamic acid, tartaric acid, citric acid, benzoic acid and the like; and among the esters of strong inorganic acids and organic sulfonic acids are those such as methyl iodide, ethyl bromide, n-propyl bromide, methyl sulfate, benzyl chloride, methyl .para-toluenesulfonate, and the like.

The following examples will illustrate specific embodiments of the invention.

EXAMPLES I. Tertiary-amino-z-arylalkanenitriles ice-cooled solution of 200 g. (1.7 moles) of phenylacetonitrile in 500 ml. of dry benzene. The

' temperature rises to about 40" C. as the sodium costing, and easy to handle.

, ives excellent results:

salt forms. After stirring for one hour, 180 g. (1.2 moles) of 3-dimethylamino-2-propyl chloride is added at a rate suflicient to keep the temperature at 30-35 C. while employing strong external cooling. Stirring is continued for four hours and then water added cautiously. The basic products are extracted from the benzene layer with 2 N hydrochloric acid, liberated with sodium hydroxide solution, and extracted with ether. After drying the ether solution over anhydrous calcium sulfate, the ether is removed by distillation and the remaining material is distilled in vacuo, the main fraction, a colorless oil, distilling at 109-11" C. at 0.8 mm., n =1.5046. This oil (89% yield) is a mixture of 4-dimethylamino-2-phenylpentanenitrile and 4-dimethylamino 3-methy1 2 phenylbutanenitrile. The mixture is used as such in subsequent condition with 4-ha1oquinolines.

When Z-diethylaminoethyl chloride or 2-dimethylaminoethyl chloride is substituted for 3- dimethylamino-Z-propyl chloride in the foregoing process, about 90% yields of 4 -diethylamino- 2-phenylbutanenitrile, B. P. 123 C. at 0.7 mm.,

- tuted-phenylacetonitrile, the corresponding tertiary-amino-2 -(substituted phenyl) acetonitrile results. For example, the condensation of 4- .chlorophenylacetonitrile, 3,4-dichlorophenylacetonitrile, or 4-methoxyphenylacetonitrile with 2- diethylaminoethyl chloride results in the formation or the corresponding 4-diethylamino 2-(substituted-phenyl) -butanenitriles (see Kwartler and Lucas, J. A. C. S. 68, 2395 (1946), who describe these intermediate nitriles as well as 5 diethylamino-2-(4-chlorophenyl)pentanenitrile which also can be used as an intermediate in our invention).

II. Tertiary-amino-Z-aryl-Z-(4-quinolyl)alkane- I nitriles These basic nitriles are prepared by condensing alkanenitrile as described in section I in the presence of a strong base. In practicing our invention, we prefer to use, as the strong base, sodium amide, which is readily available, low However, other strong bases, such as potassium amide, sodium hydride, phenyl lithium, and the like are usable in this process. The following general procedure 2-aralalkanenitrile (0.5 mole) in a 2-liter, 3-

necked flask fitted with a stirrer, thermometer.

and drying tube is added 28 g. of fresh, powdered sodium amide. Externalcooling is applied when necessary to keep the temperature ofthe reac-'- tion mixture below 45 C. At the end of about two to three hours, the temperature drops to room temperature and stirring is continued for an additional four to five hours. Water is'added cautiously, the mixture shaken vigorously; and the benzene layer separated, washed with water, dried over anhydrous calcium sulfate and filtered with decolorizing charcoal. Removal of the benzene by distillation leaves a practically quantitative yiel'dof the basic product. Where the'bases are obtained as viscous oils, crystallization is induced by stirring the oil with a little ether. Recrystallization from petroleum ether yields pure samples of the terti'ary-amino-2-aryl-2 (4-quinolyl) -alkanenitril'es as White crystalline. solids.

It. is important, in the above reaction, that the sodium amide be reasonably fresh. When sodium amide that had been stored for long periods of time (about six months) is used, the reaction fails tov go to, completion even after twenty-fourhours.

In order to remove any unreacted starting-materials, a modification of the above procedure is employed. The benzene layer, after Washing with water, is extracted with 3 N hydrochloric "acid and the combined acid extracts are made justv neutral to litmus with dilute sodium hydroxide solution. After extraction with ether to remove any unchanged 4-haloquinoline, the neutral solution is treated with excess sodium hydroxide solution and the product is taken up in chloroform. Removal of the chloroform gives the crude base which is worked up as above.

The mono-hydrochlorides of these tertiaryamino-Z-aryl 2 (4 quinolyl) alkanenitriles are prepared by dissolving the base in three tofour volumes of warm isopropanol and adding slightly less than the calculated amount of ethanolic hydrogen chloride. In some instances ether is added to turbidity and the solution scratched to induce crystallization. The hydrochlorides are dried at 120 in vacuo.

Some basic nitriles' prepared in the above manner are those having the formula and having the melting points. given in Table I TABLE I I Hydrochlo- I Base M.P R O.(corr.) %f gb5' Appcars to exist in two crystalline modifications. When first isolated it melted at 96-104" 0.

When the foregoing'procedu're is employed using as the reactants 4-diethylamino-2-(t-chlorophenyDbutanenitrile and 4,7-dichloroquinoline, the resulting product is 4-diethyla'mino-2-(4- chlorophenyl) 2 ('7 chloro 4 quinolyllbutanenitrile, M. P. 108.9-110.6' (corn).

Strong basic condensing agents other than sodium amide can be used to'prepare the tertiarycrystalline solids are separated.

amino -2-aryl-2- (4-quinolyl) alkanenitriles of our invention. For example, we foundphenyllithium and sodium hydride to beeffective, however, the resultant yields of desiredbasic nitrile are considerably less than when sodium amide is used. Examples using these two condensing agents follow: i

Phenyllithium is prepared under nitrogen by the action of 1.53 g. (0.22 mole) of lithium metal on 11.3 g. (0.1 mole) of chlorobenzene in ether,

according to standard procedures (Gilman et al.

J. A. C. S. 55, 1252 (1.933) and Method for Preparation of Organo Lithium Compounds, pamphlet, CX-SE: Form 10, Lithaloys Corp, 444 Madlson Ave., New'York' 22, N. Y.) However, it is'to be noted that there is a considerable amount 'of lithium which fails to react because of a black coating that forms on the surface of the metal. After removal of the unreacted lithium with tweezers, a solution of 21 g. (0.1 mole) of 4-diethy1amino-2-phenylbutanenitrile in 50 ml. of

ether is added, there being a heat of reaction that slight excess of sodium hydride in dry benzene are refluxed forsixteen hours. After working up according to the previously described procedure using sodium'amide as the condensing agent, a 27% yield of 4 diethylamino-2-phenyl-2(7-- ch1oro-4- quinolyl)butanenitrile is obtained. Note that the sodium hydride used in this run was the last of a bottle which has stood for some time. Possible deterioration of the sodium hydride may account for the low yield. f i -In addition-the following tertiary-amino -2- aryl-2-(4-quinolyl) -alkanenitriles are formed using the above general procedure by. condensing the appropriate tertiary-amino-2-arylalkanenitrile with the appropriate 4-haloquinoline: 4- diethylamino 2 (4 methoxyphenyl) 2 (6- methoxy 4 quinolyl) butanenitrile, 5 diethylamino 2 (4-chlorophenyl) -2(6,8-dichloro-4- quin'olyl)pentanenitrile, 4 (4 morpholinyll-Z- 3,4 dichlorophenyl) -2-(3 -nitro-4-quinolyl)buchloride and phenylacetonitrileaccording to diectionsgivenxin Example I) a mixture of'condensation products is obtained. For example,

condensation of 190 g. (0.94 mole) of. dimeth-ylamino-2-phenylalkanenitrile (the above referred to mixture) andI-g. (0.94 mole) of 4,7-dichloroquinoline using sodium amide, according to the general directions given above, yields 330 g; (0.91

mole): "of viscous: oil; from which three white The oilis warmed and poured slowly into 1.5 liters of rapidly stirred ether. After stirring for three hours, the light tan solid which separates is filtered off; yield is 115 g., M. P. 138-160 C. (fraction A). Trituration of the crude solid for twenty minutes with boiling petroleum ether (B. P. 60-68 C.) yields 46 g. of product, M. P. 165-169 C. Two recrystallizations from 600 ml. portions of absolute ethanolyields 32 g. of white rhombic plates, M. P. 182-183.8 C. (corr.), the structure of which is discussed below.

The ether filtrate, after the removal of fraction A, is treated with excess ethanolic hydrogen chloride and the ether decanted from the oil which separates. Two liters of acetone are added to the oil, and the mixture refluxed and triturated to give a yellow-orange solid which is collected by filtration (fraction B). The solid is dissolved in water, filtered with charcoal, and the free base liberated from the filtrate by means of sodium bicarbonate solution. The base is taken up in ether, the ether solution dried, filtered with charcoal, and evaporated. The remaining oil is dissolved in 200 ml. of benzene and allowed to stand for five hours. The solid that separates (35 g., M. P. 146-149" C.) is dissolved in 350 ml. of absolute ethanol and the solution filtered hot with charcoal. On cooling, 22 g. of white prismatic crystals separates; M. P. 151-152 C. corr.). (A mixed melting point with a sample isolated from fraction A is 136-143 C.) The structure of this compound is discussed below.

The acetone filtrate, after the removal of fraction B, is evaporated, the resulting oil dissolved in water, the free base liberated with alkali solution and taken up in a large volume of ether. After drying of the ether solution, the ether is removed by distillation to give an oil which is slurried with asmall volume of fresh ether to give 9 g. of a'white solid, M. P; 135-140 C. (fraction C). The product is heated with 1'75 ml. of petroleum ether (B. P. 60-68 C.) and the mixture filtered while hot. On, cooling, the filtrate yields 3 g. of pale yellow solid which is recrystallized, with charcoaling, from petroleum ether to give 2 g. of white prisms, M. P. 142-144 C., which CaHs (CHiiiNCHCHiCHCN CQHI (CHdINCHICHHCN they have eitherFormula VIII or IX:

CeHl crmmnom-ti-cn c N vIn llo s ormmcmn-b-cn I H:

thestructure of the other of VIII and IX.

In. rertiam-dmiho z-eryz-z-(4-quinozyz) allcanamides These basic amides are prepared by partially hydrolyzing' the corresponding basic nitriles described in section II. The following general procedure gives excellent results: i

A solution of one part by weight of a tertiaryamino-2-aryl-2 ;(4-quinolyl) alkanenitrile as described in section II in four volumes of concentrated sulfuric acid is allowed to stand at room temperature for fourto five weeks. The yellow solution is poured onto ice, treated with an excess of sodium hydroxide solution, and extracted with chloroform. The extract is dried over anhydrous. calcium sulfate, filtered with charcoal, and the chloroform removed by distillation to leave the crude amide in yields of or better. Becrystallation from. benzene or toluene yields, as a white crystalline solid, a tertiary-amino-Z aryl-2- ,(4-quinolyl) -alkanamide.

The monohydrochlorides of these basic amides are prepared by a, procedure similar to that used in the preparation of the corresponding salts of the basic nitriles. Larger volumes (5-20) of is0- propanol are required to dissolve the amides. The salts are recrystallized from ethanol and dried at C. in vacuo.

some basic amides prepared in the above manner are those having the formula and having the melting points given in Table II:

. TABLE II Base Hydrochloride, M. P.[C. M. P./C.

17s. 8-175 (corr.)- 254 -255 20a -2o4 220 -222 (com) 248 -249 6 247.5-248 (corr) 176. 5-173. 5 (0011.) 225 226 147. 5-148. 5 237. 4-238. 2 (corn) With decomposition.

1 Exists in a lower melting solvated form, M. P. 90-92 0., when recrystallized from benzene.

In addition, the following tertiary-amino-2-, aryl-2-(4-quinolyl) -alkanamides are formed by partially hydrolyzing the corresponding basic nitriles: 4 diethylamino 2- (4 methoxyphenyl) 2 (6 {methox'y' 4 quinolyD-butanamide, diethylainino 2 (4 chlorophenyl) 2 (6,8 d-ichloro 4 quinoIyD- pentanamide, 4 "(4 inorpholinyl) 2 (3,4 dichlorophenyl) 2 (3 nitro 4 quinolyD- butanamide, and 4 (-2 methyl 1 piperidyl) 2" phenyl 2 (3 methyl 7 iodo 4 quinolyllbutanamide.

The partial hydrolysis of the basic nitriles to the corresponding basic amides can be effected other reaction conditions. For example, when '4 diethylamino-z phenyl-2 (7-chloro 4 quin olyllbutanenitrile is allowed to stand for only and: ha e physica "constants given in Table'IILM a rxpL III 1 R R Base, M.P. or s. P.'/ 0. he Hydrochloride, M. 1 o.

' M.P.90.2-916 (corr.).

155.5-1565. l .01 on. 13.1 1508.1; 0.1 micron 6200' 200.6'201.4(6i-r2).

, 1', CE W P. 77.8-79.2 (corn)- 1 B. P. 154 at 0.1 micron 1.6124 can B. P. 190 at05mm- 1; 5942 176.4=l77;4 corn-y cm. B. P. 209 at 0.8 1.6052 134-184.; 00112). v v i q l .6-16L6 corn; taken fast Bin-155's at 1-5986 {loss-1915mm; taken singly).

byrefluxm the nitrile with an equal weight of sodium hydroxide in eight volumes of 70% ethanoi for twelve hours or by heating 5 g. of the nitrile, 8 m1. of water and 8 m1. of concentrated Sulfuric acid at reflux temperature for one hour. 1V. Teriiary-amino-i -ary'l-1'- (4 q'uinlyl) alkanes These basic compounds are obtained from the dorresponding basic nitriles as described in .section by complete hydrolysis of the nitrile group to the carboxyl group which spontaneously loses carbon dioxide. The following generai procedure gives excellent results:

A; solution of 30 g. of a ter'tiary-amino 2 'aryl- 2*(4-Q'uin'olyl) -'allanenitri1e in ml. of water and -50 ml. of concentrated sulfuric acid is re= mixed for 12 to 48 hours. The completeness of the reaction can be determined by passing nitrogal-ever the 'surtace or the reaction mixture and bubbling the escaping gases through barium hydroxide solution. When no cloudiness results after a minute or so, the reaction is regarded as complete. The reaction mixture is poured onto ice containing an excess of sodium hydroxide solution, the liberated base extracted with ether, and the ether extract dried, filtered with charcoal and evaporated to give a pale yellow oil. In some instances a small amount of intermediate basic amide (described in Example HI) is isolated even after a reflux -period of 48 hours. This is removed by dissolving the oil'in petroleum" ether (B. P. -68 0.), seeding with the amide, and allowing the mixture to stand for 24 hours. Evaporation of the filtered solution yields the desired tertiary-amino l -"arylal (4=quinolyllal kane, which can be converted into the hydrochloride Without further purineatio 'or distilled in va'eue to give paleyello'w tinted oils.

The monohydrochlorides are prepared by dissolving the free base in three volumes at isopiopanol and adding slightly less than the equivalent amount of alcoholic hydrogen chloride. In order to induce crystallization, ether is added "to turbidity, thevinside pf the flaskscratched, and

In addition, the following tertiary-amino-laryl-1-(4-quinolyl) alkanes are formed using the above general procedure of completely hydrolyzing the corresponding basic nitriles to the -related carboxylic acids which. spontaneously lose carbon dioxide: 3-diethy1amino-1-(4-methoxyphenyl) -l(6-methoxy-4 quinolyl) propane, '4-*di= ethylamino-l- (4-chlorophenyl) -.l-(6,-8-dichloro- 4,-quinolyl) butane, 3-(4-morpholinyl) -1-(3,4-dich1orophenyl)1+( 3-nitro 4 quinolyl) propane, and 3-(2 methyl 1 piperidyl).-l-phenyle1--(3- methyl-7-chloro+4-quinoly1)propane.

The tertiary-amino 2 aryl-2-jfi4-quinolyllal kanamides which-are illustrated in. Example 111 above are described and claimed in our copending divisional application Serial No. 196,521, filed N0? vember 18, 1950, and the.tertiary-amino-l-aryl- 1-(4-quinoly1) alkanes which are illustrated in Example IV above are described and claimed in our copending divisional application Serial No; 196,522, filed November 18, 1950.

We claim:

1. A compound selected from the group -eonsisting of basic compounds having the formula A s x-t en where B is a lower aliphatic tertiary-amino radical, X is a lower alkylene radical, A is an aryl radical of the benzene series and Q is a 4-quinolyl radical, which comprises reacting a 4-haloquinoline of the formula Q-halogen with a basic alphaarylalkanenitrile of the formula BXCH(A) CN in the presence of astrong'ba'se.

' 3. A compound selected from the group consisting of basic compounds having. the formula Q where B is a lower aliphatic tertiary-amino radical, X is a lower alkylene radical, and Q is a 4- quinolyl radical, and acid addition salts thereof.

4. A compound selected from the group consisting of 4-dimethylamino-2-pheny1-2- (l-chloro- -quinolyDbulanenitrile and acid addition salts thereof.

5. A compound selected from the group consisting of 4-diethylamino-2-pheny1-2-('l-chloro- 4-quinolyl)butanenitrile and acid addition salts thereof.

6. A compound selected from the group consisting of 4-diethylamino-2-(4-ch1orophenyl) -2- (7-ch1oro-4-quinolyl) butanenitrile and acid addition salts thereof.

7. A compound selected from the group consisting of 4-dimethylamino-2-phenyl-2- '7-ch1oro- 4-quinolyl)pentanenitrile and acid addition salts thereof.

8. A compound selected from the group consisting of 4-dimethylamino-3-methyl-2-pheny1- 2-(7-chloro-4-quinolyl) butanenitrile and acid addition salts thereof.

9. A process for preparing a compound having the formula where B is a lower aliphatic tertiary-amino radi- 14 cal, X is a lower 'alkylene radical and Q is a 4- quinolyl radical, which comprises reacting a 4- haloquinoline of the formula Q -halogen with a basic alpha-pheny1a1kanenitrile of the formula BXCH(C6H5) CN in the presence of a strong base.

10. A process for preparing -dimethylamino- 2-pheny1-2-(7-ch1oro 4 quinolyhbutanenitrile which comprise reacting 4,7-dichloroquinoline with 4-dimethylamino-2-phenyl-butanenitrile in the presence of sodium amide.

11. A process for preparing 4-diethylamino-2- pheny1-2-(7 -chloro 4- quinolyDbutanenitrile which comprises reacting 4,7-dichloroquinoline with 4-diethylamino-2-phenylbutanenitrile in the presence of sodium amide.

12. A process for preparing 4-diethylamino-2- (4-ch1orophenyl) -2- (7-chloro-4-quinolyl) butanenitrile which comprises reacting 4,7-dich1oroquinoline with 4-diethylamino-2-(l-chlorophenyl)- butanenitrile in the presence of sodium amide.

13. A process for preparing 4-dimethylamino- 2 phenyl-2 (7-ch1oro-4-quinolyl) pentanenitrile which comprises reacting 4,7-dich10roquinoline with 4-dimethylamino-Z-phenylpentanenitrile in the presence of sodium amide.

14. A process for preparing 4-dimethylamino- 3 methyl 2-phenyl-2-(7-chloro-4-quinolyDbutanenitrile which comprises reacting 4,7-dichloroquinoline with 4 dimethylamino 3-methy1-2- phenylbutanenitrile in the presence of sodium amide.

ALEXANDER R. SURREY. ROYAL A. CUTLER.

No references cited. 

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF BASIC COMPOUND HAVING THE FORMULA 